It is well established that certain forms of hydrocarbons require upgrading in order to either transport them or enhance value for sale. Further, conventional refineries are not suited to processing heavy oil, bitumen etc. and thus the viscosity, density and impurity content, such as heavy metals, sulfur and nitrogen, present in such heavy materials must be altered to permit refining. Upgrading is primarily focused upon reducing viscosity, sulfur, metals, and asphaltene content in the bitumen.
One of the problems with heavy oil and bitumen upgrading is that the asphaltenes and the heavy fraction must be removed or modified to create value and product yield. Typical upgraders exacerbate the problem by the formation of petcoke or residuum which results in undesirable waste material. This material, since it cannot be easily converted by conventional methods, is commonly removed from the process, reducing the overall yield of valuable hydrocarbon material from the upgrading process.
The Fischer-Tropsch process has found significant utility in hydrocarbon synthesis procedures and fuel synthesis. The process has been used for decades to assist in the formulation of hydrocarbons from several materials such as coal, residuum, petcoke, and biomass. In the last several years, the conversion of alternate energy resources has become of great interest, given the escalating environmental concerns regarding pollution, the decline of world conventional hydrocarbon resources, and the increasing concern over tailings pond management, together with the increasing costs to extract, upgrade and refine the heavy hydrocarbon resources. The major producers in the area of synthetic fuels have expanded the art significantly in this technological area with a number of patented advances and pending applications in the form of publications. Applicant's co-pending U.S. application Ser. No. 13/024,925, teaches a fuel synthesis protocol.
Examples of recent advances that have been made in this area of technology includes the features taught in U.S. Pat. No. 6,958,363, issued to Espinoza, et al., Oct. 25, 2005, Bayle et al., in U.S. Pat. No. 7,214,720, issued May 8, 2007, U.S. Pat. No. 6,696,501, issued Feb. 24, 2004, to Schanke et al.
In respect of other progress that has been made in this field of technology, the art is replete with significant advances in, not only gasification of solid carbon feeds, but also methodology for the preparation of syngas, management of hydrogen and carbon monoxide in a XTL plant, the Fischer-Tropsch reactors management of hydrogen, and the conversion of carbon based feedstock into hydrocarbon liquid transportation fuels, inter alia. The following is a representative list of other such references. This includes: U.S. Pat. Nos. 7,776,114; 6,765,025; 6,512,018; 6,147,126; 6,133,328; 7,855,235; 7,846,979; 6,147,126; 7,004,985; 6,048,449; 7,208,530; 6,730,285; 6,872,753, as well as United States Patent Application Publication Nos. US2010/0113624; US2004/0181313; US2010/0036181; US2010/0216898; US2008/0021122; US 2008/0115415; and US 2010/0000153.
The Fischer-Tropsch (FT) process has several significant benefits when applied to a bitumen upgrader process, one benefit being that it is able to convert previously generated petcoke and residuum to valuable, high quality synthetic crude oil (SCO) and high quality refined products with notably increased paraffinic content. A further significant benefit is that the raw bitumen yield to refined products is near or greater than 100%, more specifically greater than 130% yield, a 35% to 65% product yield increase relative to certain current upgrader processes. Another benefit is that there is no petcoke and residuum waste product to impact the environment thus improving overall bitumen resource utilization.
A further benefit of the application of the FT process to a bitumen upgrader is that the FT byproducts can be partially and fully blended with the distilled, separated or treated fractions of the bitumen or heavy oil feed stream to formulate and enhance the quality of refinery products such as diesel and jet fuel. The significant overall benefit is the carbon conversion efficiency is greater than 90%, providing significant reduction in facility GHG emissions and 100% conversion of the bitumen or heavy oil resource without the formation of wasteful byproducts.
A further benefit of the application of the FT process to a bitumen upgrader is that a sweet, highly paraffinic and high cetane content synthetic diesel (syndiesel) is produced. More specifically, beneficial byproducts of the FT process such as paraffinic naphtha and FT vapours (such as methane and liquid petroleum gases (LPG)), have particular value within the bitumen upgrader process and upstream unit operations. FT vapours, virtually free from sulfur compounds can be used as upgrader fuel or as feedstock for hydrogen generation to offset the requirement for natural gas. FT naphtha, primarily paraffinic in nature, can also be used in the generation of hydrogen, but further, due to its unique paraffinic nature, it can also be used as an efficient deasphalting solvent not readily available from current upgrader operations.
It has also been well documented that the use of FT paraffinic naphtha as a solvent for an oil sands froth unit improves the operation and efficacy of fine tailings and water removal at a reduced diluent to bitumen (D/B) ratio and relatively low vapour pressure. This has significant advantages in terms of lowering the size and cost of expensive separators and settlers and increasing their separation performance and capacity rating. This results in virtually dry bitumen froth feed (<0.5 basic sediment and water) to the upgrader, while improving impact on the tailings pond.
Having thus generally discussed the appropriateness of the Fischer-Tropsch technique in synthesizing syngas to FT liquids, a discussion of the prior art and particularly the art related to the upgrading and gasifying of heavy hydrocarbon feeds would be useful.
One of the examples in this area of the prior art is the teachings of U.S. Pat. No. 7,407,571 issued Aug. 5, 2008, to Rettger et. al. This reference names Ormat Industries Ltd. as the Assignee and teaches a process for producing sweet synthetic crude oil from a heavy hydrocarbon feed. In the method, the patentees indicate that heavy hydrocarbon is upgraded to produce a distillate feed which includes sour products and high carbon byproducts. The high carbon content byproducts are gasified in a gasifier to produce a syngas and sour byproducts. The process further hydroprocesses the sour products along with hydrogen gas to produce gas and a sweet crude. Hydrogen is recovered in a recovery unit from the synthetic fuel gas. The process also indicates that further hydrogen gas is processed and hydrogen depleted synthetic fuel gas is also produced. Further hydrogen gas is supplied to the hydroprocessing unit and a gasifying step is conducted in the presence of air or oxygen. The gas mixture is scrubbed to produce a sour water and a clean sour gas mixture. The sour gas mixture is subsequently processed to produce a sweet synthetic fuel gas and a hydrogen enriched gas mixture from the synthetic fuel gas using a membrane. The overall process is quite effective, however, it does not take advantage of the conversion of synthesized streams which are useful for introduction into the hydroprocessing unit for production of synthetic crude, the recycling of unique streams for use in the upgrader, nor is there any teaching specifically of the integration of the Fischer-Tropsch process or the recognition of the benefit to the process of using a SMR and/or ATR in the process circuit to maximize SCO yields and reducing dependence on natural gas.
Iqbal et. al. in U.S. Pat. No. 7,381,320 issued Jun. 3, 2008, teaches a process for heavy oil and bitumen upgrading. In overview, the process is capable of upgrading crude oil from a subterranean reservoir. The process involves converting asphaltenes to steam power, fuel gas, or a combination of these for use in producing heavy oil or bitumen from a reservoir. A portion of the heavy oil or bitumen are solvent deasphalted to form an asphaltene fraction and a deasphalted oil, referred to in the art as DAO as a fraction free of asphaltenes and with reduced metals content. The asphaltene fraction from the solvent deasphalting is supplied to the asphaltenes conversion unit and a feed comprising the DAO fraction supplied to a reaction zone of a fluid catalytic cracking (FCC) unit with an FCC catalyst to capture a portion of the metals from the DAO fraction. A hydrocarbon effluent is recovered from this having a reduced metal content. Similar to the process taught in U.S. Pat. No. 7,407,571, this process has utility, however, it limits the conversion of the otherwise wasteful asphaltene to production of solid fuel or pellets or conversion to syngas for fuel, hydrogen or electric power production. There is no teaching specifically integrating the Fischer-Tropsch process.
In U.S. Pat. No. 7,708,877 issued May 4, 2010 to Farshid et. al. there is taught an integrated heavy oil upgrader process and in line hydro finishing process. In the process, a hydroconversion slurry reactor system is taught that permits a catalyst, unconverted oil and converted oil to circulate in a continuous mixture throughout a reactor with no confinement of the mixture. The mixture is partially separated between the reactors to remove only the converted oil while allowing unconverted oil in the slurry catalyst to continue on to the next sequential reactor where a portion of the unconverted oil is converted to a lower boiling point. Additional hydro processing occurs in additional reactors for full conversion of the oil. The so called fully converted oil is subsequently hydrofinished for nearly complete removal of heteroatoms such as sulfur and nitrogen.
This document is primarily concerned with hydroconversion of heavy hydrocarbon, while not being suitable for bitumen upgrading. It also fails to provide any teaching regarding the use of Fischer-Tropsch process, usefulness of recycle streams, hydrogen generation or other valuable and efficient unit operations critical to successful upgrading of raw bitumen.
Calderon et. al. in U.S. Pat. No. 7,413,647 issued Aug. 19, 2008, teach a method and apparatus for upgrading bituminous material. The method involves a series of four distinct components, namely a fractionator, a heavy gas oil catalytic treater, a catalyst regenerator/gasifier and a gas clean up assembly. The patent indicates that in practicing the method, the bitumen in liquid form is fed to the fractionator for primary separation of fractions with the bulk of the bitumen leaving the bottom of the fractionator in the form of a heavy gas oil which is subsequently pumped to the catalytic treater and sprayed on a hot catalyst to crack the heavy gas oil, thus releasing hydrocarbons in the form of hydrogen rich volatile matter while depositing carbon on the catalyst. The volatile matter from the treater is passed to the fractionator where condensable fractions are separated from noncondensable hydrogen rich gas. The carbon containing catalyst from the treater is recycled to the regenerator/gasifier and the catalyst, after being regenerated is fed hot to the treater.
The method does not incorporate the particularly valuable Fischer-Tropsch process or provide a unit for effecting the Fischer-Tropsch reaction and further, the method is limited by the use of the catalyst which would appear to be quite susceptible to sulfur damage and from this sense there is no real provision for handling the sulfur in the bitumen.
In United States Patent Application, Publication No. US 2009/0200209, published Aug. 13, 2009, Sury et. al. teach upgrading bitumen in a paraffinic froth treatment process. The method involves adding a solvent to a bitumen froth emulsion to induce a settling rate of at least a portion of the asphaltenes and mineral solids present in the emulsion and results in the generation of the solvent bitumen-froth mixture. Water droplets are added to the solvent bitumen-froth mixture to increase the rate of settling of the asphaltenes and mineral solids. The focus of the publication is primarily to deal with the froth. There is no significant advance in the upgrading of the bitumen.
A wealth of advantages are derivable from the technology that has been developed and which is described herein. These are realized in a number of ways including:                a) near 100% or greater yield of total refinery products slate from heavy oil or bitumen without the wasteful production of petcoke or residuum;        b) high quality synthetic hydrocarbon byproducts such as synthetic naphtha, syndiesel, synjet, synthetic lubes and synthetic wax is produced to highest quality commercial standards;        c) maximum utilization of carbon in heavy oil and bitumen to form high quality synthetic hydrocarbon byproducts, with the significant reduction (greater than 50%) in GHG from the facility;        d) the distilled and treated streams are substantially void of undesirable chemical and physical properties such as heavy metals, sulfur, Conradson Carbon (CCR) and naphthenic acid (TAN number);        e) less natural gas is required to generate hydrogen for upgrading as the FT naphtha, refinery fuel gas, LPG, FT vapours and hydroprocessing vapours can be recycled to generate a hydrogen rich syngas;        f) pure hydrogen can be generated from the hydrogen rich syngas using membranes, absorption or pressure swing adsorption units, for use in the hydroprocessing (hydrocracking, isomerisation, hydrotreating) units;        g) Fischer-Tropsch (FT) liquids are primarily paraffinic in nature improving the quality and value of refinery product slate;        h) FT naphtha is rarely available in any quantity in current upgraders and would be very preferentially used for deasphalting distilled bottoms in a Solvent Deasphalting Unit (SDA) and in a oil sands Froth Treatment Unit; and        i) concentrated CO2 is available from the gasifier (XTL) syngas treatment unit, allowing the upgrader to be a low cost carbon capture ready CO2 source for carbon capture and sequestration (CCS) projects.        
As part of the further advancements that are within the ambit of the technology set forth herein, the refinery aspect is addressed.
In this embodiment of the invention, a process is elucidated to fully upgrade light crude oil typically having an API density of between 22 and 40 and heavy oil with an API density of between 12 to 22 or extra heavy oil or bitumen with a density of less than API 12 API without the production of undesirable hydrocarbon byproduct, such as petcoke, heavy fuel oil or asphalt. The process combines the Fischer Tropsch hydrocarbon synthesis unit with conventional refinery processing steps to produce full commercial specification refined products, such as, but not limited to, naphtha for petrochemicals feedstock, naphtha for gasoline blending, gasoline, diesel, jet fuel, lubricants, wax, inter alia.
Generally, conventional or simple topping, hydroskimming and light conversion refineries are designed to receive sweet or sour light crude oils>22 API, more specifically 30 to 40 API density for the production of refined fuels. Light refineries are primarily focused on production of gasoline, jet and diesel fuel and if required, the refinery will manage refinery bottoms as asphalt or fuel oil sales. Usually the volume of bottoms is minimal for crude densities greater than 30 API.
In recent years the supply and availability of light crude oil has fallen appreciably and become very costly relative to discounted heavier crude costs. Many conventional refineries have been recently reconfigured to medium conversion refineries to accept further lower cost heavy crude oils (20 to 30 API) resulting in higher fractions of the crude oil converting to residue and being converted to asphalt, sour heavy fuel oil or petcoke. In addition, many refineries have been forced to further upgrade the hydrotreating facilities to produce ultra-low sulfur gasoline (ULSG) and ultra-low sulfur diesel (ULSD) to meet tighter regulatory commercial market specifications. Economics of these modified refineries have become very challenging due to significant capital and processing costs without additional product yield or significant revenue gain.
To further complicate issues, the large volumes of low value world crude oil supplies now take the form of extra heavy crude (12 to 22 API) or bitumen (6 to 11 API) sources from in situ or mining oilsands operations. Complex refinery conversions are now required, involving the addition of deep conversion refinery units such as deep hydrocracking and coking, to accommodate the extra heavy oil and bitumen feeds. These deep conversion refineries, are capital intense and produce significantly lower value byproducts such as petcoke with significant increased emissions of GHG (Green House Gases). Refinery product yields based on extra heavy and bitumen crude oil are about 80 to 90 volume %.
Petcoke has undesirable properties, such as difficult and costly handling, storage and transportation requirements, major environmental impact and contains high levels of sulfur (6+ wt %) as well as toxic heavy metals such as nickel and vanadium (1000 ppm+). Therefore petcoke has limited markets and is often a commercial and environmental liability as it is stored or marketed at very low or negative returns.
As the world oil supply transitions more towards the supply of extra heavy oil (12 to 20 API) and bitumen (6 to 12 API), the vacuum bottoms approaches 60 vol % of the whole crude assay. Accordingly, there is a need for an improved process to convert all the heavy oil and bitumen feed to commercial high value product without the production of byproducts such as petcoke and CO2 (GHG), with reduced impact on the environment.
The refinery process to be discussed addresses the needs in this area. Advantages attributable to the process include:                a) Transformation of refinery bottoms, typically >950+ F material to synthetic fuels such as FT naphtha, synthetic diesel, synthetic jet fuel, synthetic lube oils, waxes, etc.;        b) Elimination of the production of low value hydrocarbon byproducts such as heavy fuel oil, road asphalt and petcoke, resulting in full (100 wt %) utilization of the crude feed regardless of density or blended densities of crude slate;        c) Retention and conversion of greater than 90% of all carbon in the feed streams (i.e. crude oil, natural gas, etc) resulting in greater than 50% reduction in CO2 or GHG emissions; and        d) Substantial reduction of the Conradson Carbon (CCR), Naphthenic Acid (TAN) and heavy metals and significant amount of sulfur from the main conventional refinery processes. This is advantageous since it permits the use of lower cost, conventional hydroprocessing units (hydrocrackers) with single or multiple fixed bed catalyst systems to upgrade the heavy fractions to high value refinery fuels.        